EP3017075B1 - Hydrolyzed starches as grinding aids for mineral ore processing - Google Patents
Hydrolyzed starches as grinding aids for mineral ore processing Download PDFInfo
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- EP3017075B1 EP3017075B1 EP14747168.4A EP14747168A EP3017075B1 EP 3017075 B1 EP3017075 B1 EP 3017075B1 EP 14747168 A EP14747168 A EP 14747168A EP 3017075 B1 EP3017075 B1 EP 3017075B1
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- mineral ore
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- 239000010931 gold Substances 0.000 claims description 22
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- 229910019142 PO4 Inorganic materials 0.000 claims description 4
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- YCAGGFXSFQFVQL-UHFFFAOYSA-N Endothion Chemical compound COC1=COC(CSP(=O)(OC)OC)=CC1=O YCAGGFXSFQFVQL-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C17/00—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls
- B02C17/18—Details
- B02C17/183—Feeding or discharging devices
- B02C17/186—Adding fluid, other than for crushing by fluid energy
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C19/00—Other disintegrating devices or methods
- B02C19/0056—Other disintegrating devices or methods specially adapted for specific materials not otherwise provided for
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C23/00—Auxiliary methods or auxiliary devices or accessories specially adapted for crushing or disintegrating not provided for in preceding groups or not specially adapted to apparatus covered by a single preceding group
- B02C23/18—Adding fluid, other than for crushing or disintegrating by fluid energy
Definitions
- the invention relates to the use of compositions which enhance the effectiveness of grinding mineral ore slurry.
- the compositions comprise hydrolyzed starch.
- the compositions are added to mineral ore slurry prior to or during the process of comminuting the mineral ore in a mineral mining process.
- the mineral industry is a large consumer of chemicals which are used during many stages of the processing of mineral ore. For example, chemicals are added to facilitate grinding of large chunks of mineral ore into finer particles of ore. Once the ore has been reduced to the appropriate size, the mineral fines can be extracted and transformed into a useful product.
- the grinding of mineral ore is a very energy intensive and inefficient stage of mineral ore processing.
- mechanical and chemical adaptations have been developed to facilitate the comminution of mineral ore.
- One such adaptation is the introduction of chemicals which are effective in making the grinding process more efficient. These classes of chemicals can generally be referred to as grinding aids. Grinding aids can directly lower the energy of the comminution (i.e. grinding) process and allow for more efficient throughput of mineral ore.
- These chemical additives also have been shown to increase the level of fines produced during the grinding stage thus increasing efficiency.
- US 2,145,206 A discloses a method of floating carbonaceous precious metal ores, which comprises subjecting an aqueous pulp of a carbonaceous precious metal ore to froth flotation in the presence of a dextrin.
- US 3,796,308 A discloses that finely ground impure metal sulfides or pyritic ores, particularly coals, are upgraded by surface oxidation of the metal sulfide or pyritic material by selected bacteria, e.g. from the Thiobacillus-Ferrobacillus group, to render the surface hydrophilic, followed by a particle separation step from an aqueous slurry e.g. selective agglomeration or flotation.
- compositions useful as grinding aids in mining operations comprise hydrolyzed starch. These compositions are typically added to mineral slurry prior to or during a grinding stage in a mineral ore recovery process.
- the invention encompasses use of a composition comprising a hydrolyzed starch for reducing the stickiness, energy of grinding, yield stress and/or the viscosity of an aqueous mineral ore slurry during a grinding stage in a mineral ore recovery process, wherein the composition is added to the aqueous mineral ore slurry prior to or during the grinding stage.
- hydrolyzed starch increases the capacity and throughput of mineral ores during the grinding stage in mining processes, particularly in recovery of mineral fines from ore. This will benefit operations by decreasing downtime and moving more ore through the comminution process in shorter time periods. Improvement in ore slurry flow-ability at a given throughput will result in reduction of ore slurry pumping energy for ore discharged from the mill and transported to the next destination point in a mill circuit.
- Useful hydrolyzed starches include non-ionic low molecular weight species.
- the grinding aid compositions comprise hydrolyzed starch selected from the group consisting of dextrin, maltodextrin, corn syrup solids, and the like, and combinations thereof.
- the grinding aid composition may consist or consist essentially of the hydrolyzed starch.
- grinding is the process in a commercial mining operation in which larger fragments of ore are broken down to particles of very fine particle sizes, i.e. the fines.
- the valuable minerals are extracted from the fines.
- the grinding process occurs in one or more means for comminuting mineral ore, such as ball mills, rod mills, autogenous mills, semi-autogenous (“SAG”) mills, pebble mills, high pressure grinding mills, burhstone mills, vertical shift impactor mills, tower mills and the like.
- Ball mills, SAG mills, rod mills and high pressure grinding roll mills are preferably used in industrial mining operations.
- the grinding aid composition facilitates the comminution of the mineral ore fragments in the mineral ore slurry thus allowing grinding to the desired particle size with less energy requirements.
- the grinding aid composition also affects the rheology of the mineral ore slurry allowing it to flow within the mill better, with less agglomeration, allowing more efficient grinding of the mineral ore. Further, because the hydrolyzed starch affects the rheological properties of the mineral ore slurry and improves flow-ability, the invention also facilitates flow and pump-ability of the slurry that discharges from a means for comminuting the mineral ore.
- the hydrolyzed starch improves the flow-ability of the ground mineral ore in pipes or other conduits and through pumps as the slurry is moved from the means for comminuting the mineral ore to other unit operations in a mining circuit and improves flow-ability and processability in unit operations downstream of the grinding operation.
- the mineral ore slurry comprising water and mineral ore is added to the mill either continuously, such as through a feed pipe, or manually.
- the grinding aid composition is added to the mineral ore slurry either prior to the mineral ore slurry entering a grinding chamber(s) of the mill, such as in the feed pipe, prior to comminution or is added to the slurry when the slurry is in a grinding chamber(s) of the mill.
- the grinding aid composition can be added to the mineral ore slurry both prior to the mineral ore slurry entering the mill and while the mineral ore slurry is in the grinding chamber(s) of the mill.
- the grinding aid composition is applied in a method of wet grinding a mineral ore comprising adding an effective amount of a grinding aid comprising a hydrolyzed starch, such as those discussed above, to an aqueous slurry comprising the mineral ore and grinding the mineral ore with a means for comminuting the mineral ore, such as the aforementioned mills.
- the typical mineral ores comprise base metals, precious metals or combinations of these.
- Some examples of minerals in base metals or precious metals that may comprise the mineral ore include a mineral selected from the group consisting of gold, aluminum, silver, platinum, copper, nickel, zinc, lead, molybdenum, iron, and the like, and combinations thereof.
- Other materials that may comprise the mineral ore include phosphate, coal, and the like, and combinations thereof.
- the grinding aid composition is added to the mineral slurry, which is the aqueous slurry comprising the mineral ore, in an amount of about 0.005% to about 1.0% by dry weight of the mineral ore, preferably in an amount of about 0.01% to about 0.40% by dry weight of the mineral ore.
- the grinding aid composition is effective at a variety of solids content of the mineral slurry, typically, the solids content of the mineral slurry, that is the amount of mineral ore (mineral ore content) in the slurry, is at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70% or at least about 80%, such as about 50% to about 90%, like as about 60% to 80%.
- Persons of ordinary skill in these arts, after reading this disclosure, will appreciate that all ranges and values for the amount of grinding aid composition and solids content are contemplated.
- the grinding aid composition decreases the stickiness of the mineral ore slurry while the ore fragments are being comminuted in the means for comminution.
- the grinding aid compositions are also found to adjust the particle size distribution of the mineral ore in the slurry.
- the dispersion affect of grinding aid composition allows the slurry to flow while the slurry is in the means for comminution so that impact in the means for comminution, such as between the ore particles and the balls in the mill, occur more frequently allowing for more effective grinding.
- the hydrolyzed starches particularly those which are low molecular weight non-ionic oligomers, are assessed as grinding additives in the examples below.
- An all-direction planetary ball mill, model XBM4X-VL, from Col-Int Tech, Columbia, South Carolina, USA was used for ore grinding.
- Four 1 liter stainless steel (SS) cups were placed in cup fixtures mounted onto a rotating disk turned 45° degrees to align the long axis of the cups horizontally to mimic a larger scale industrial ball mill orientation.
- Each cup was spun in opposite direction with respect to the disk rotation to create planetary motion during the grinding tests.
- the energy of grinding was adjusted by pre setting the frequency for the motor input as well as the duration of the test.
- the ground mineral ore/mineral ore slurry was analyzed for particle size distribution, stickiness, yield stress and viscosity using the following analytical procedures.
- the size distribution of particles was analyzed using a HELOS dry particle size analyzer from Sympatec GmbH, Clausthal-Zellerfield, Germany in accordance with manufacturer's instructions.
- This particle sizing method is based on an analysis of the angular dependence of light scattered from an optically dilute dispersed phase sample.
- the measuring instrument comprises a forward scattering angle photo ring diode detector and a number of discrete higher forward and back scattering angle photodiode detectors.
- the angular dependence of the scattered light is measured at two discrete wavelengths and a particle size distribution is iteratively generated to replicate the measured scattering profile. Average particle sizes (mean and median) and particle size distributions of powder are determined.
- the specific surface area of the material is calculated assuming the particles are solid, homogeneous spheres.
- the particle size distribution was calculated by placing a powder sample of dried comminuted mineral, about 1/2 teaspoon in volume, on the vibrating table of the HELOS dry particle size analyzer. The sample was automatically dispersed through the laser system and the distribution curve was calculated automatically through the software embedded in the analyzer. Entire cumulative size distributions with mean numbers were summarized.
- the grinding balls were removed from the cups leaving only slurry comprising ground ore in the containers.
- Four containers comprising the slurry were weighed.
- the slurries were then dumped from the containers by inverting the containers and lightly tapping the bottom of the each container two times.
- the following procedure was used to measure the power draw of a ball mill grinder.
- the sample preparation procedure used in the Stickiness measurement was used in the Energy of Grinding procedure.
- a Universal Power Cell (Model: UPC), was connected on one end to the motor of the lab ball mill and the other end to a computer having a WinDaqTM program (other similar programs may be used for this), that is capable of measuring the power draw during ball mill operation.
- Dynamic yield stress and apparent viscosity for mineral slurries prepared with and without grinding aid compositions were measured using TA Discovery HR-2 controlled stress rheometer with parallel plate's geometry from TA Instruments, Wilmington, Delaware, USA.
- the set up of the rheometer was similar to the one described in C. F. Ferraris, "Measurements of the rheological properties of cement paste: a new approach", NIST, in proceedings of RILEM Intern. Symposium, March, 1999 , which is incorporated herein by reference in its entirety, for rheology measurements of cement pastes with both top/rotating and bottom/stationary plates made with serrated pattern having a depth of serration about 450 microns. This geometry prevents slippage during the measurements and gives very accurate yield stress readings. A gap of 1000 micron was used.
- Dynamic yield stress and apparent viscosity at a given shear rate are the essential rheological characteristics to mimic slurry flow-ability in industrial ball mills with the shear rates selected in the range, about 13 s -1 (reciprocal or inverse seconds) to about 730 s -1 .
- the slurry samples were vigorously shaken by hand at a constant pace for about 5 minutes and then immediately measured.
- the measuring protocol for shear stress - shear rate (using the TA Trios program from TA Instruments) included starting at zero (s -1 ) ramping up to 2000 (s -1 ) with 20 seconds/point, tested using linear scale and testing was repeated 2 times for each sample with 2 samples made in duplicate, hence providing 4 data points altogether for reporting an average dynamic yield stress and apparent viscosity.
- the shear stress versus shear rate curve (its linear segment at low shear rates) is extrapolated to zero shear rate with the y-intercept giving dynamic yield stress value. This is essentially a Bingham plastic flow curve analysis as described in T. Chen, "Rheological techniques for yield stress analysis", TA Instruments Application Paper - AAN017, which is incorporated herein by reference in its entirety.
- Gold ore with the particle size distribution characterized by 100% of the material below 3/8 of an inch was obtained from a North American mine and dried to remove residual moisture. The gold ore was ground applying the equipment and procedures described above. The ground samples were then tested for particle size distribution, stickiness, yield stress and viscosity using the analytical procedures described above. The results are summarized in Table 1 below. The data in Table 1 represents an average of 2 to 4 repetitive runs. Table 1 % Slurry Amount of Ore (gram) Amt. of Water Total Slurry Wt.
- the slurry at 50% by weight is very fluid and visually inform.
- the slurry remains fluid at 60% by weight, while there is some heterogeneity observed.
- Increasing the solids content to 70% by weight resulted in a strong jump in slurry viscosity that looked fairly viscous and non-uniform with reaching paste-like behavior at 80% solids content by weight.
- Ore slurry stickiness, viscosity and yield stress undergo dramatic jump above 60% by weight of slurry concentration indicating strong agglomeration of ground ore and increase in cohesive/adhesive forces.
- the particle size distribution of ground gold ore as measured by HELOS dry particle size analyzer showed a fairly uniform pattern with medium particle size around 20 micron with the largest size fraction of about 70 micron to about 100 micron representing less than 10% of ground material. There was no effect of slurry concentration on the ground, dry ore particle size distribution within the experimental error, resulting in a mean particle size of 20 micron as shown in Table 2 for gold ore. Note that in Table 2 Additive refers to the grinding aid composition.
- maltodextrin in an amount of 0.02% by dry weight of the mineral ore was added to 150 grams (gm) of gold ore that is the same as described above for Example 1 and 64 grams of water to make a slurry having a 70% mineral ore content as set forth in Table 3.
- Maltodextrin, in dry form (MD 01956), from Cargill, Incorporated, Minneapolis, Minnesota, USA (“Cargill”) was used, which is noted in the Additive column in Table 3.
- the slurry was ground using the equipment and procedures described above.
- the ground ore was analyzed for stickiness, viscosity and yield stress using the procedures described above.
- the analytical results for this example are summarized in Table 3 below with reference to the maltodextrin Additive.
- maltodextrin is effective in controlling gold ore slurry flow-ability which can result in improved throughput of ore grinding without negative issues, such as increased ore stickiness and viscosity.
- High ore stickiness can result in ball mill motor bearing damage due to agglomerated ore drop and weight impact during balling.
- the ore with high viscosity and stickiness is very difficult to discharge from a ball mill and would be impossible to transport to the next point downstream in a commercial mining operation.
- gold ore excessive agglomeration can result in less effective grinding of ore reflected in a larger fraction of coarser material.
- the particle size distribution was essentially the same for the final ground ore with the grinding aid compositions and controls without any such additive.
- the grinding aid compositions provide for beneficial rheological properties which will facilitate commercial mining grinding and throughput to subsequent unit operations in the mining process.
- the grinding aid composition comprised dextrin in dry powder, Dextrin Plus 8702 from Cargill, which is noted in the Additive column in Table 3.
- the dextrin was incorporated through addition to water phase prior to ball mill testing.
- Dextrin in an amount of 0.02% by dry weight of the mineral ore was added to 150 grams of gold ore that is the same as described above for Example 1 and 64 grams of water to make slurry having a 70% by weight mineral ore content as set forth in Table 3.
- the slurry was ground using the equipment and procedures described above.
- the ground ore was analyzed for stickiness, viscosity and yield stress using the procedures described above.
- the grinding aid composition comprised corn syrup solids, Star Dry Corn Syrup 42C from Tate & Lyle PLC, London, United Kingdom, which is noted in the Additive column in Table 3.
- the corn syrup solids were incorporated through addition to water phase prior to ball mill testing.
- Corn syrup solids in an amount of 0.02% by dry weight of the mineral ore was added to 150 grams of gold ore, that is the same as described above for Example 1, and 64 grams of water to make a slurry having 70% by weight mineral ore content as set forth in Table 3.
- the slurry was ground using the equipment and procedures described above.
- the ground ore was analyzed for stickiness, viscosity and yield stress using the procedures described above.
- Grinding aid composition comprising maltodextrin (MD 01956 from Cargill as identified as Additive in Table 4) was used with the gold ore slurry in an amount of 0.1% by dry weight of mineral ore as shown in Table 4 to make slurry having 80% by weight mineral ore content.
- the slurry was ground using the equipment and procedures described above.
- the ground ore was analyzed using the procedures described above and the results, along with the results for some comparative examples where no grinding aid was used with gold ore, are set forth in Table 4.
- the resultant slurry shows extreme (100%) stickiness, paste-like behavior with very high viscosity and yield stress.
- 0.1% maltodextrin by dry weight of the mineral ore results in substantial change in ground slurry characteristics, i.e. decrease in stickiness, viscosity and yield stress.
- the slurry starts to show flow-ability, approaching the behavior of 70% by weight mineral ore slurry without additives, hence reinforcing strong anti-agglomerating benefits of the maltodextrin.
- the grinding aid compositions tested in this example resulted in reduced ore stickiness, yield stress and viscosity, as shown in Table 7.
- the pH and average pre-grind particle size are set forth in Table 2.
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Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201361842188P | 2013-07-02 | 2013-07-02 | |
PCT/US2014/041540 WO2015002720A1 (en) | 2013-07-02 | 2014-06-09 | Hydrolyzed starches as grinding aids for mineral ore processing |
Publications (2)
Publication Number | Publication Date |
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EP3017075A1 EP3017075A1 (en) | 2016-05-11 |
EP3017075B1 true EP3017075B1 (en) | 2021-08-04 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP14747168.4A Active EP3017075B1 (en) | 2013-07-02 | 2014-06-09 | Hydrolyzed starches as grinding aids for mineral ore processing |
Country Status (10)
Country | Link |
---|---|
US (1) | US10774399B2 (es) |
EP (1) | EP3017075B1 (es) |
CN (1) | CN105431560A (es) |
AU (1) | AU2014284673B2 (es) |
BR (1) | BR112015031849B1 (es) |
CA (1) | CA2915825C (es) |
CL (1) | CL2015003795A1 (es) |
MX (1) | MX2015017084A (es) |
PE (1) | PE20160572A1 (es) |
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US2145206A (en) * | 1938-02-01 | 1939-01-24 | American Cyanamid Co | Depression of carbonaceous material in flotation |
US3339730A (en) * | 1962-07-14 | 1967-09-05 | Column Flotation Co Of Canada | Froth flotation method with counter-current separation |
US3796308A (en) * | 1972-07-24 | 1974-03-12 | Canadian Patents Dev | Bacterial oxidation in upgrading sulfidic ores and coals |
GB1449268A (en) * | 1973-11-20 | 1976-09-15 | Ici Ltd | Treatment process |
US4274599A (en) | 1977-11-21 | 1981-06-23 | The Dow Chemical Company | Ore grinding process including a grinding aid of an anionic polyelectrolyte |
US5131600A (en) | 1989-02-13 | 1992-07-21 | The Dow Chemical Company | Alkanol amine grinding aids |
US5328690A (en) | 1991-02-21 | 1994-07-12 | University Of South Alabama | Polyamino acid dispersants |
US5799882A (en) | 1996-02-21 | 1998-09-01 | Klimpel; Richard R. | Hydroxy-carboxylic acid grinding aids |
EP1894213A4 (en) * | 2005-06-09 | 2009-07-15 | Nat Starch Chem Corp | AQUEOUS PRINTABLE ELECTRICAL LADDER |
JP2008163412A (ja) * | 2006-12-28 | 2008-07-17 | Jtekt Corp | 鉄系粉末材料及びその製法、並びに製鋼原料用ブリケット |
FR2913426B1 (fr) | 2007-03-05 | 2009-06-05 | Coatex Soc Par Actions Simplif | Utilisation comme agent de rheologie dans une pate plastique chargee,d'un carbonate de calcium broye a sec avec un copolymere de l'acide (meth) acrylique avec une fonction alcoxy ou hydroxy polyalkyleneglycol. |
CN101337204B (zh) * | 2008-08-13 | 2011-03-30 | 中南大学 | 一种双季铵盐类化合物在硅酸盐矿物浮选上的应用及硅酸盐矿物浮选捕收剂 |
SI2455429T1 (sl) | 2010-11-19 | 2013-12-31 | Omya International Ag | Postopek za pripravo vodne suspenzije mineralnih snovi z uporabo aminov, kombiniranih z vinil karboksilnimi polimeri |
WO2014139904A1 (en) * | 2013-03-13 | 2014-09-18 | Akzo Nobel Chemicals International B.V. | Rheology modifiers |
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MX2015017084A (es) | 2016-04-13 |
US10774399B2 (en) | 2020-09-15 |
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CN105431560A (zh) | 2016-03-23 |
WO2015002720A1 (en) | 2015-01-08 |
AU2014284673A1 (en) | 2015-12-24 |
US20150008272A1 (en) | 2015-01-08 |
WO2015002720A4 (en) | 2015-03-12 |
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